JP4484131B2 - Film for flat panel display - Google Patents

Description

（式中、Ｒ₁ 〜Ｒ₄ は、各々独立して、水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基を表す。これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。）
【００１０】
【化６】

（式中、Ｒ₅ 〜Ｒ₈ は、各々独立して、水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。Ｒ₉ 〜Ｒ₁₂は、各々独立して、水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。Ｒ₁₃は炭素数１〜６の脂肪族基を表すか単に結合を表す。Ｘは、−SiO(Ｒ₁₄)(Ｒ₁₅）−および／または−SiO(Ｒ₁₆)(Ｒ₁₇）−の単独重合体、ブロックまたはランダム共重合体を表し、重合度は０〜２００であり、Ｒ₁₄〜Ｒ₁₇は、各々独立して、水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。）
【００１１】
【化７】

（式中、Ｒ₁₈〜Ｒ₁₉は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。Ｙは、
【化８】

であり、ここにＲ₂₀，Ｒ₂₁は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数６〜１２のアリール基を表すか、Ｒ₂₀とＲ₂₁が一緒に結合して、炭素数３〜６の炭素環または複素環を形成する基を表し、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。ａは０〜２０の整数を表す。）
【００１２】
本発明のフラットパネルディスプレー用フィルムに用いられるポリカーボネート樹脂は、前記一般式（Ａ）と一般式（Ｂ）、または一般式（Ａ）と一般式（Ｂ）と一般式（Ｃ）の化合物とを、炭酸エステル形成化合物と反応させることによって、製造することができるものであり、ビスフェノールＡから誘導されるポリカーボネートを製造する際に用いられている公知の方法、例えばビスフェノール類とホスゲンとの直接反応（ホスゲン法）、あるいはビスフェノール類とビスアリールカーボネートとのエステル交換反応（エステル交換法）などの方法を採用することができる。
【００１３】
本発明中の炭酸エステル形成性化合物としては、例えばホスゲンや、ジフェニルカーボネート、ジ−ｐ−トリルカーボネート、フェニル−ｐ−トリルカーボネート、ジ−ｐ−クロロフェニルカーボネート、ジナフチルカーボネートなどのビスアリルカーボネートが挙げられる。これらの化合物は２種類以上併用して使用することも可能である。
【００１４】
本発明に用いられる一般式（Ａ）の化合物としては、具体的には、９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、３，６−ジメチル−９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−メトキシ−４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−エトキシ−４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−エチル−４−ヒドロキシフェニル）フルオレン、４，５−ジメチル−９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−フェニル−４−ヒドロキシフェニル）フルオレン、３，６−ジメチル−９，９−ビス（３−メチル−４−ヒドロキシフェニル）フルオレン及び３，６−ジフェニル−９，９−ビス（４−ヒドロキシフェニル）フルオレン等を挙げることができる。中でも特に、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレンが好ましい。これらの化合物は２種類以上併用して使用することも可能である。
【００１５】
本発明に用いられる一般式（Ｂ）の化合物としては、具体的には、下記のものが例示される。
【００１６】
【化９】

【００１７】
これらは、２種類以上併用することも可能である。Ｘには、ジメチルシロキサンが１〜１００個またはジフェニルシロキサンが１〜１００個含まれるものおよびそれらのランダム共重合体が好ましい。中でも、特に、α，ω−ビス[3-(o-ヒドロキシフェニル）プロピル］ポリジメチルジフェニルランダム共重合シロキサン、α，ω−ビス[3-(o-ヒドロキシフェニル）プロピル］ポリジメチルシロキサンが好ましい。
【００１８】
本発明中の一般式（Ｃ）の化合物としては、具体的には、4,4'−ビフェニルジオール、ビス（4-ヒドロキシフェニル）メタン、ビス（4-ヒドロキシフェニル）エーテル、ビス（4-ヒドロキシフェニル）スルホン、ビス（4-ヒドロキシ−3-メチルフェニル）スルホン、ビス（4-ヒドロキシフェニル）スルホキシド、ビス（4-ヒドロキシフェニル）スルファイド、ビス（4-ヒドロキシフェニル）ケトン、1,1-ビス（4-ヒドロキシフェニル）エタン、2,2-ビス（4-ヒドロキシフェニル）プロパン（ビスフェノ−ルＡ；BPA)、2,2-ビス（4-ヒドロキシフェニル）ブタン、1,1-ビス（4-ヒドロキシフェニル）シクロヘキサン（ビスフェノ−ルＺ；BPZ)、2,2-ビス（4-ヒドロキシ−3-メチルフェニル）プロパン（ジメチルビスフェノールＡ）、2,2-ビス（4-ヒドロキシ−3,5-ジメチルフェニル）プロパン、1,1-ビス（4-ヒドロキシフェニル）−1-フェニルエタン（ビスフェノールＡＰ；BPAP）、ビス（4-ヒドロキシフェニル）ジフェニルメタン、2,2-ビス（4-ヒドロキシ−3-アリルフェニル）プロパン、3,3,5-トリメチル−1,1-ビス（4-ヒドロキシフェニル）シクロヘキサン（トリメチルビスフェノール−Ｚ；TMBPZ)などが例示される。これらは、２種類以上併用することも可能である。また、これらの中でも特に2,2-ビス（4-ヒドロキシフェニル）プロパンが好ましい。
【００１９】
ホスゲン法とエステル交換法では、一般式（Ａ）の化合物および一般式（Ｂ）の化合物の反応性を考慮した場合、ホスゲン法の方が好ましい。
【００２０】
前者のホスゲン法においては、通常酸結合剤および溶媒の存在下において、本発明における一般式（Ａ）の化合物と一般式（Ｂ）の化合物、または一般式（Ａ）の化合物と一般式（Ｂ）の化合物と一般式（Ｃ）の化合物とを、ホスゲンと反応させる。酸結合剤としては、例えばピリジンや、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物などが用いられる。また、溶媒としては、例えば塩化メチレン、クロロホルム、クロロベンゼン、キシレンなどが用いられる。さらに、縮重合反応の触媒として、トリエチルアミンのような第三級アミンなどが使用される。重合度調節には、フェノール、ｐ−ｔ−ブチルフェノール、p-クミルフェノール、アルキル置換フェノール類、ヒドロキシ安息香酸アルキル類やアルキルオキシフェノール類などの一官能基化合物を分子量調節剤として加える。さらにまた、所望に応じ、亜硫酸ナトリウム、ハイドロサルファイトなどの酸化防止剤や、フロログルシン、イサチンビスフェノール、1,1,1-トリス（4-ヒドロキシフェニル）エタン、α，α',α"-トリス（4-ヒドロキシフェニル)-1,3,5-トリイソプロピルベンゼンなど分岐化剤を小量添加してもよい。反応は通常０〜１５０℃、好ましくは５〜４０℃の範囲とするのが適当である。反応時間は反応温度によって左右されるが、通常０．５分〜１０時間、好ましくは１分〜２時間である。また、反応中は、反応系のｐＨを１０以上に保持することが望ましい。
【００２１】
一方、後者のエステル交換法においては、本発明における一般式（Ａ）の化合物と一般式（Ｂ）の化合物または一般式（Ａ）の化合物と一般式（Ｂ）の化合物と一般式（Ｃ）の化合物とをビスアリールカーボネートと混合し、減圧下で高温において反応させる。この時、フェノール、ｐ−ｔ−ブチルフェノール、p-クミルフェノール、アルキル置換フェノール類、ヒドロキシ安息香酸アルキル類やアルキルオキシフェノール類などの一官能基化合物を分子量調節剤として加えてもよい。反応は通常１５０〜３５０℃、好ましくは２００〜３００℃の範囲の温度において行われ、また減圧度は最終で好ましくは１mmHg以下にして、エステル交換反応により生成した該ビスアリールカーボネートから由来するフェノール類を系外へ留去させる。反応時間は反応温度や減圧度などによって左右されるが、通常１〜１０時間程度である。反応は窒素やアルゴンなどの不活性ガス雰囲気下で行うことが好ましく、また、所望に応じ、酸化防止剤や分岐化剤を添加して反応を行ってもよい。
【００２２】
本発明においてホスゲン法を採用する場合は、用いられる三級アミン重合触媒として、例えばトリエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン、Ｎ，Ｎ’―ジメチルシクロヘキシルアミン、Ｎ，Ｎ’―ジエチルアニリン、ジエチルアミノピリジン等があるが、触媒活性や洗浄除去の問題からトリエチルアミンが好ましい。重合触媒の添加量は、使用される全ビスフェノール類に対して、 0.001〜５mol%が好ましい。
【００２３】
本発明においてホスゲン法を採用する場合は、反応を効率よく行うため第四級アンモニウム塩を少量添加してもよい。具体的には、テトラメチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、テトラ−ｎ−ブチルアンモニウムアイオダイドなどが例示され、これらのうちトリメチルベンジルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライドが好ましい。この第四級アンモニウム塩は、使用される全ビスフェノール類に対して、一般に0.0005〜５mol%使用されることが好ましい。
【００２４】
更に、本発明に分子量調節剤を用いる場合には、特に一価フェノールが好ましく、具体的にはフェノールやブチルフェノール、オクチルフェノール、ノニルフェノール、デカニルフェノール、テトラデカニルフェノール、ヘプタデカニルフェノール、オクタデカニルフェノール等のアルキル置換フェノール；ヒドロキシ安息香酸ブチル、ヒドロキシ安息香酸オクチル、ヒドロキシ安息香酸ノニル、ヒドロキシ安息香酸デカニル、ヒドロキシ安息香酸ヘプタデカニル等のヒドロキシ安息香酸アルキルエステル；ブトキシフェノール、オクチルオキシフェノール、ノニルオキシフェノール、デカニルオキシフェノール、テトラデカニルオキシフェノール、ヘプタデカニルオキシフェノール、オクタデカニルオキシフェノール等のアルキルオキシフェノール類が例示される。この分子量調節剤の添加量は全ビスフェノール類に対して０．１〜５０ｍｏｌ％である。好ましくは、０．５〜１０mol%である。
【００２５】
これらの反応で合成された本発明のポリカーボネート樹脂は、フラットパネルディスプレー用フィルムとして成形するための溶融押出フィルム成形、射出フィルム成形、圧縮フィルム成形、湿式フィルム成形など公知の成形法で成形可能であるが、溶融押出フィルム成形により、フラットパネルディスプレー用フィルムとして成形されるには、容易に溶融押出フィルム成形できることが望ましく、極限粘度が０．２〜１．０ｄｌ／ｇの範囲であることが好ましい。
【００２６】
また、前記一般式（Ｂ）の使用量はフラットパネルディスプレー用フィルムの強度を考慮すると、前記一般式（Ａ）及び一般式（Ｂ）及び一般式（Ｃ）の合計量に対して２０〜６０重量％が好ましい。前記一般式（Ｂ）が２０重量％未満では、剛直に成りすぎて脆く、６０重量％を越えるとフラットパネルディスプレー用フィルムとして必要な耐熱性が不足する。
【００２７】
前記一般式（Ｃ）の使用は、諸性能の向上やコスト低減等のため使用可能であるが、特にビスフェノールＡを用いた場合、従来のビスフェノールＡ型ポリカーボネートとの相溶性がよく、リサイクル性や他品種押出機内の樹脂置換性が向上する利点を有する。フラットパネルディスプレー用フィルムの偏光（位相差）を考慮すると、前記一般式（Ｃ）は、前記一般式（Ａ）及び一般式（Ｃ）の合計量に対して５０重量％未満が好ましい。前記一般式（Ｃ）が前記一般式（Ａ）及び一般式（Ｃ）の合計量に対して５０重量％以上では偏光（位相差）が著しく悪化し不充分となる。
【００２８】
本発明のポリカーボネート樹脂は、従来のフラットパネルディスプレー用フィルムの材料であるポリカーボネート樹脂と同様に高度に精製されたものが好ましい。具体的には、直径５０μｍ以上のダストが実質上検出されず、直径０．５〜５０μｍのダストが３×１０⁴ 以下、無機および有機残留塩素が２ｐｐｍ以下、残留アルカリ金属が２ｐｐｍ以下、残存水酸基２００ｐｐｍ以下、残存窒素量５ｐｐｍ以下、残存モノマー２０ｐｐｍ以下等の基準を可能な限り満たすように精製される。また、低分子量体除去や溶媒除去のため抽出等の後処理が行われる場合もある。また、原材料の一般式（Ａ）、一般式（Ｂ）および一般式（Ｃ）の化合物や炭酸エステル形成化合物等についても不純物や異性体などを極力低減した材料を用いることが好ましい。
【００２９】
本発明のポリカーボネート樹脂は、フラットパネルディスプレー用フィルム成形時に必要な安定性や離型性を確保するため、所望に応じて、ヒンダードフェノール系やホスファイト系酸化防止剤；シリコン系、脂肪酸エステル系、脂肪酸系、脂肪酸グリセリド系、密ろう等天然油脂などの滑剤や離型剤；ベンゾトリアゾール系、ベンゾフェノン系、ジベンゾイルメタン系、サリチレート系等の光安定剤；ポリアルキレングリコール、脂肪酸グリセリド等帯電防止剤などを適宜併用してよい。
【００３０】
さらにはコスト低減等の目的で、本発明のポリカーボネート樹脂と従来のビスフェノールＡ型ポリカーボネートと性能を損なわない範囲で任意に混合して使用する事も可能である。
【００３１】
本発明のポリカーボネート樹脂を用いたフラットパネルディスプレー用フィルムは、通常溶融押出フィルム成形で成形する場合には、２３０〜３８０℃の範囲で成形されることが好ましく、溶融粘度が高化式フローテスター(280℃、15.7MPa 、ノズル径1mm ×10mm）の１×１０^-2cc/sec以上であることがあることが好ましい。１×１０^-2cc/sec未満では溶融粘度が大きすぎるため押出が難しく、成形温度や分子量により調整し、物性を損なわない範囲で成形可能な流動性を得ることが好ましい。
【００３２】
【実施例】
次に実施例により、本発明をさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
【００３３】
実施例１
8.8%(w/v) の水酸化ナトリウム水溶液４９リットルに9,9-ビス（4-ヒドロキシ−3-メチルフェニル）フルオレン３．５kg（以下、BCFLと略称）とハイドロサルファイト10g を加え溶解した。これにメチレンクロライド２５リットルを加え、15℃に保ちながら撹拌しつつ、ホスゲン２．３kgを30分かけて吹き込んだ。
吹き込み終了後、１分間激しく撹拌して反応液を乳化させ、p-ターシャルブチルフェノール８４g （以下PTBPと略称）と下記ポリシロキサン化合物３．５kg（以下Si1 と略称）とを加え、さらに１０分間撹拌後、20mlのトリエチルアミンを加え、さらに６０分撹拌を継続し重合させた。
【００３４】
【化１０】

【００３５】
重合液を水相と有機相に分離し、有機相をリン酸で中和し、洗液の導電率が10μＳ/cm 以下になるまで水洗を繰り返した後、精製樹脂液を得た。得られた精製樹脂液０．５μｍ径テフロンフィルターで濾過後、強攪拌されている６０℃の純水に樹脂液をゆっくり滴下し、溶媒を除去しつつ重合物を固形化した。固形物を濾過後、乾燥して白色粉末状重合体を得た。
【００３６】
この重合体は、メチレンクロライドを溶媒とする濃度0.5g／dlの溶液の温度20℃（ハギンズ定数0.45）における極限粘度［η］は0.38dl／g であった。
【００３７】
得られたポリカーボネート粉末にステアリン酸モノグリセリド300ppmを添加し、50μｍポリマーフィルターを付けたベント付き５０ｍｍ押出機にて２８０℃で押出し、溶融ペレット化を行った。
【００３８】
得られたペレットを、水平３本ロールを備えたベント付き９０ｍｍ溶融フィルム押出機にて２８０℃で押出し、溶融成形フィルムを得た。
得られたポリカーボネートフィルムの厚さは１０２μｍで、幅方向の厚みムラは±３μｍであった。
【００３９】
実施例２
Si1 の代わりに下記ポリシロキサン化合物２．３Kg（以下Si2 と略称）に変更し、PTBPを４８g に変更し、さらにBCFL投入と同時にトリエチルベンジルアンモニウムクロライド0.5g加えた以外は実施例１と同様に重合反応を行った。
【００４０】
【化１１】

【００４１】
得られた重合体の極限粘度［η］は0.28dl/gであった。実施例１と同様にペレット化後、得られた溶融成形ポリカーボネートフィルムの厚さは１０１μｍで、幅方向の厚みムラは±３μｍであった。
【００４２】
実施例３
Si1 の代わりに下記ポリシロキサン化合物３．５Kg（以下Si3 と略称）に変更し、PTBPの代わりにフェノール４８g （以下PHと略称）に変更した以外は実施例１と同様に重合反応を行った。
【００４３】
【化１２】

【００４４】
得られた重合体の極限粘度［η］は0.29dl／g であった。実施例１と同様にペレット化後、得られた溶融成形ポリカーボネートフィルムの厚さは９９μｍで、幅方向の厚みムラは±３μｍであった。
【００４５】
実施例４
BCFLを２．５kg、Si1 を１．８kgに変更し、さらにBCFL投入と同時に2,2-ビス（4-ヒドロキシフェニル）プロパン０．６０kg（以下、BPA と略称）を加えた以外は、実施例１と同様に重合反応を行った。
得られた重合体の極限粘度［η］は0.35dl／g であった。実施例１と同様にペレット化後、得られた溶融成形ポリカーボネートフィルムの厚さは１０１μｍで、幅方向の厚みムラは±３μｍであった。
【００４６】
比較例１
実施例１のポリカーボネートの代わりに、市販のビスフェノールＡ型光学用ポリカーボネート樹脂（三菱瓦斯化学（株）製ユーピロH-4000）を用いた以外は実施例１と同様にペレット化した。得られた溶融成形ポリカーボネートフィルムの厚さは１００μｍで、幅方向の厚みムラは±３μｍであった。
【００４７】
比較例２
BCFLの代わりに、9,9-ビス（4-ヒドロキシフェニル）フルオレン0.65kg（以下BFLと略称）とBPA3.8kgを用い、PTBPを90g に変更し、Si1 を用いなかった以外は、実施例１と同様に反応重合を行った。
得られた重合体の極限粘度［η］は0.32dl／g であった。実施例１と同様にペレット化後、得られた溶融成形ポリカーボネートフィルムの厚さは１０２μｍで、幅方向の厚みムラは±３μｍであった。
【００４８】
比較例３
BCFLの代わりに、3,3,5-トリメチル−1,1-ビス（4-ヒドロキシフェニル）シクロヘキサン0.87kg（以下TMBPZ と略称）とBPA3.6kgを用い、PTBPを92g に変更し、Si1 を用いなかった以外は、実施例１と同様に反応重合を行った。
得られた重合体の極限粘度［η］は0.31dl／g であった。実施例１と同様にペレット化後、得られた溶融成形ポリカーボネートフィルムの厚さは１００μｍで、幅方向の厚みムラは±３μｍであった。
【００４９】
実施例１〜４及び比較例１〜３の各試験後の外観、偏光板の間に挟んでの透過率の結果を表１に示す。偏光板の間に挟んでの透過率の測定は各試験片が位相差をどのくらい起こしているかを確認する評価である。偏光軸を合わせた２枚の偏光板の間に偏光軸と試験片の延伸方向（シートのＭＤ方向、巻き取り方向）を合わせ挟んだ構成を（α）とし、偏光軸と試験片の延伸軸（シートのＭＤ方向、巻き取り方向）を45°傾けて挟んだ構成を（β）とする。試験片が偏光（位相差）を起こしていても偏光軸と樹脂の配向軸が一致していれば偏光状態は崩れず、偏光（位相差）による透過率低下は無い。しかし、偏光軸と樹脂の配向軸が45°傾けると、位相差を起こし偏光状態が崩れ透過率は低下する。このため（α）と（β）の値が大きく異なるほど、偏光（位相差）を起こしているシートとなる。
【００５０】
【表１】

【００５１】
ＢＣＦＬ：９，９−ビス（３−メチル4-ヒドロキシフェニル）フルオレン
ＢＰＡ：２，２−ビス（４−ヒドロキシフェニル）プロパン
ＢＦＬ：９，９−ビス（４−ヒドロキシフェニル）フルオレン
TMBPZ:3,3,5-トリメチル−1,1-ビス（4-ヒドロキシフェニル）シクロヘキサン
極限粘度：0.5g／100mlジクロロメタン樹脂溶液を20℃、ハギンズ定数 0.45 で極限粘度［η］(dl/g)を求めた。
透過率：スガ試験器（株）製 HGM-2DPを用いて測定(JIS K 6714)を行った。
【００５２】
【発明の効果】
本発明より、偏光（位相差）が少なく、好みに応じた形状をフィルム面に付与可能な転写性に優れたフラットパネルディスプレー用フィルムが作成できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a film for a flat panel display that is suitably used for a flat panel display excellent in display quality such as a liquid crystal display.
[0002]
[Prior art]
In recent years, the display quality of flat panel displays such as liquid crystal displays has reached almost the same level as CRTs that have been widely used as conventional displays. As it is being developed, its field of use is expanding. It is widely used in many products such as notebook personal computers, OA such as TVs, desktop personal computers, and fax machines, home appliances, mobile phone displays such as mobile phones and PDAs.
[0003]
Polycarbonate resin derived from bisphenol A is widely used as a diffusion film which is a part of a film material constituting a liquid crystal display, taking advantage of its transparency, heat resistance and dimensional stability. became. However, there are some problems when the polycarbonate film material is used for a liquid crystal display.
[0004]
Such diffusion films are usually manufactured by melt extrusion film forming. In melt extrusion film forming, production is performed while stretching in the flow direction, so that polymer molecular chains are aligned in parallel with the stretching direction and polarized light (phase difference) is generated. When a film having such properties is used as a kind of diffusion film for a liquid crystal display, a phase difference is caused when passing through the diffusion film, the transmittance to the polarizing plate is deteriorated, and the liquid crystal screen looks dark. Also, if the degree of polarization differs depending on the location, the external light passes through the polarizing plate, enters the diffusion sheet, is reflected by the member below it, enters the diffusion sheet again, and the light transmitted through the polarizing plate becomes a rainbow pattern May be visible. This is because the diffusion sheet becomes a phase difference plate, and the phase difference varies depending on the location, so that the light interferes and looks like a rainbow pattern.
[0005]
In order not to generate such polarized light (phase difference), a technique of forming a wet film rather than a melt-extruded film is generally used (JP-A-8-054615, JP-A-8-160222). However, since the production of films by wet film forming uses an organic solvent, it is inevitable that the cost is high and the environment is adversely affected.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a flat panel display film having a small amount of polarized light (phase difference) and excellent transferability capable of imparting a desired shape to a film surface at low cost by melt extrusion film forming.
[0007]
[Means for Solving the Problems]
As a result of intensive investigations to solve the conventional problems, the present inventors have found that a copolymer polycarbonate resin derived from specific types of bisphenols is polarized (phase difference) even when melt extrusion film molding is performed. Thus, the present inventors have found that the film becomes a high-quality flat panel display film having good transferability, transparency and moldability, and has completed the present invention.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
That is, the present invention comprises reacting a compound represented by general formula (A) and general formula (B), or general formula (A), general formula (B), and general formula (C) with a carbonate ester-forming compound. The general formula (B) is 20 to 60 wt% with respect to all monomer components [general formula (A) + general formula (B) + general formula (C)], and the intrinsic viscosity. [Η] is a flat panel display film made of a polycarbonate resin having 0.2 to 1.0 [dl / g].
[0009]
[Chemical formula 5]

(In the formula, R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 represents an alkoxy group, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, (It can also have a C1-C5 alkoxy group.)
[0010]
[Chemical 6]

(In the formula, R _{5 to} R ₈ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 alkoxy groups, or aralkyl groups having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, .R ₉ to R _12, which may have an alkoxy group having 1 to 5 carbon atoms are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, carbon atoms 2 An alkenyl group having 5 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms as a substituent , An alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms .X is .R ₁₃ which may have to represent a mere bond or represents an aliphatic group having 1 to 6 carbon _{atoms, -SiO (R 14) (R} 15) - and / or -SiO (R ₁₆₎ (R ₁₇ )-represents a homopolymer, a block or a random copolymer, the degree of polymerization is 0 to 200, and R _{14 to} R ₁₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, An aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom (As a substituent, it can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group.)
[0011]
[Chemical 7]

(In the formula, R _{18 to} R ₁₉ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 alkoxy groups, or aralkyl groups having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, It can also have a C1-C5 alkoxy group, Y is
[Chemical 8]

Wherein R ₂₀ and R ₂₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or the number of carbon atoms A group having 6 to 12 aryl groups, or a group in which R ₂₀ and R ₂₁ are bonded together to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms, and these groups have carbon atoms Can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group as a substituent. a represents an integer of 0 to 20. )
[0012]
The polycarbonate resin used for the flat panel display film of the present invention is the compound represented by the general formula (A) and the general formula (B), or the general formula (A), the general formula (B), and the general formula (C). , Which can be produced by reacting with a carbonic acid ester-forming compound, and known methods used in producing polycarbonates derived from bisphenol A, such as direct reaction of bisphenols with phosgene ( A phosgene method) or a transesterification reaction (transesterification method) between a bisphenol and a bisaryl carbonate can be employed.
[0013]
Examples of the carbonic acid ester forming compound in the present invention include phosgene, bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. It is done. Two or more of these compounds can be used in combination.
[0014]
Specific examples of the compound of the general formula (A) used in the present invention include 9,9-bis (4-hydroxy-2-methylphenyl) fluorene and 9,9-bis (4-hydroxy-3-methyl). Phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methoxy-4-hydroxyphenyl) ) Fluorene, 9,9-bis (3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis (4 -Hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (3-methyl) 4-hydroxyphenyl) can be given fluorene and 3,6-diphenyl-9,9-bis (4-hydroxyphenyl) fluorene. Among these, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene are particularly preferable. preferable. Two or more of these compounds can be used in combination.
[0015]
Specific examples of the compound of the general formula (B) used in the present invention include the following.
[0016]
[Chemical 9]

[0017]
These can be used in combination of two or more. X preferably includes 1 to 100 dimethylsiloxanes or 1 to 100 diphenylsiloxanes, and random copolymers thereof. Among these, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethyldiphenyl random copolymer siloxane and α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane are particularly preferable.
[0018]
Specific examples of the compound of the general formula (C) in the present invention include 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, and bis (4-hydroxy Phenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis ( 4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxy Phenyl) cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydroxy-3-methylphenyl) propane (dimethylbisphenol A), 2,2-bis (4-hydroxy-3,5-dimethyl) Ruphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP; BPAP), bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-allylphenyl) ) Propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane (trimethylbisphenol-Z; TMBPZ) and the like. These can be used in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.
[0019]
In the phosgene method and the transesterification method, the phosgene method is preferred in consideration of the reactivity of the compound of the general formula (A) and the compound of the general formula (B).
[0020]
In the former phosgene method, the compound of the general formula (A) and the compound of the general formula (B) or the compound of the general formula (A) and the general formula (B) in the present invention usually in the presence of an acid binder and a solvent. ) And a compound of general formula (C) are reacted with phosgene. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. As the solvent, for example, methylene chloride, chloroform, chlorobenzene, xylene and the like are used. Further, a tertiary amine such as triethylamine is used as a catalyst for the condensation polymerization reaction. For the polymerization degree adjustment, monofunctional compounds such as phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols, alkyl hydroxybenzoates and alkyloxyphenols are added as molecular weight regulators. Furthermore, if desired, antioxidants such as sodium sulfite and hydrosulfite, phloroglucin, isatin bisphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-Tris A small amount of a branching agent such as (4-hydroxyphenyl) -1,3,5-triisopropylbenzene may be added, and the reaction is usually carried out in the range of 0 to 150 ° C., preferably 5 to 40 ° C. Although the reaction time depends on the reaction temperature, it is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours, and the pH of the reaction system should be maintained at 10 or more during the reaction. Is desirable.
[0021]
On the other hand, in the latter transesterification method, the compound of the general formula (A) and the compound of the general formula (B) or the compound of the general formula (A) and the compound of the general formula (B) and the general formula (C) in the present invention are used. Are mixed with bisaryl carbonate and reacted at high temperature under reduced pressure. At this time, monofunctional compounds such as phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols, alkyl hydroxybenzoates and alkyloxyphenols may be added as molecular weight regulators. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, but is usually about 1 to 10 hours. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon, and the reaction may be performed by adding an antioxidant or a branching agent as desired.
[0022]
When the phosgene method is employed in the present invention, examples of the tertiary amine polymerization catalyst used include triethylamine, tri-n-propylamine, tri-n-butylamine, N, N′-dimethylcyclohexylamine, N, N′— There are diethylaniline, diethylaminopyridine, and the like, and triethylamine is preferable from the viewpoint of catalyst activity and washing removal. The addition amount of the polymerization catalyst is preferably 0.001 to 5 mol% with respect to all bisphenols used.
[0023]
When employing the phosgene method in the present invention, a small amount of a quaternary ammonium salt may be added in order to carry out the reaction efficiently. Specific examples include tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide, and tetra-n-butylammonium iodide. Among these, trimethylbenzylammonium chloride and triethylbenzylammonium chloride are exemplified. preferable. This quaternary ammonium salt is generally preferably used in an amount of 0.0005 to 5 mol% based on the total bisphenols used.
[0024]
Further, when a molecular weight regulator is used in the present invention, monohydric phenol is particularly preferable, specifically, phenol, butylphenol, octylphenol, nonylphenol, decanylphenol, tetradecanylphenol, heptadecanylphenol, octadecanyl. Alkyl-substituted phenols such as phenol; hydroxybenzoic acid alkyl esters such as butyl hydroxybenzoate, octyl hydroxybenzoate, nonyl hydroxybenzoate, decanyl hydroxybenzoate, heptadecanyl hydroxybenzoate; butoxyphenol, octyloxyphenol, nonyloxyphenol, Alkyl oxyphenes such as decanyloxyphenol, tetradecanyloxyphenol, heptadecanyloxyphenol, octadecanyloxyphenol, etc. Nord acids are exemplified. The addition amount of this molecular weight regulator is 0.1-50 mol% with respect to all the bisphenols. Preferably, it is 0.5 to 10 mol%.
[0025]
The polycarbonate resin of the present invention synthesized by these reactions can be molded by known molding methods such as melt extrusion film molding, injection film molding, compression film molding, and wet film molding for molding as a flat panel display film. However, in order to be formed as a flat panel display film by melt extrusion film formation, it is desirable that the melt extrusion film can be easily formed, and the intrinsic viscosity is preferably in the range of 0.2 to 1.0 dl / g.
[0026]
The amount of the general formula (B) used is 20 to 60 with respect to the total amount of the general formula (A), the general formula (B), and the general formula (C) in consideration of the strength of the flat panel display film. % By weight is preferred. If the general formula (B) is less than 20% by weight, it becomes too rigid and brittle, and if it exceeds 60% by weight, the heat resistance necessary for a flat panel display film is insufficient.
[0027]
The use of the general formula (C) can be used for improving various performances, reducing costs, etc. In particular, when bisphenol A is used, the compatibility with the conventional bisphenol A type polycarbonate is good, and recyclability and It has the advantage that the resin replacement property in other types of extruders is improved. Considering the polarization (phase difference) of the flat panel display film, the general formula (C) is preferably less than 50% by weight based on the total amount of the general formula (A) and the general formula (C). When the general formula (C) is 50% by weight or more with respect to the total amount of the general formula (A) and the general formula (C), the polarization (phase difference) is remarkably deteriorated and becomes insufficient.
[0028]
The polycarbonate resin of the present invention is preferably highly purified as in the case of a polycarbonate resin which is a material for conventional flat panel display films. Specifically, dust having a diameter of 50 μm or more is substantially not detected, dust having a diameter of 0.5 to 50 μm is 3 × 10 ⁴ or less, inorganic and organic residual chlorine is 2 ppm or less, residual alkali metal is 2 ppm or less, residual hydroxyl group Refinement is performed so as to satisfy the criteria of 200 ppm or less, residual nitrogen amount of 5 ppm or less, and residual monomer of 20 ppm or less as much as possible. In some cases, post-treatment such as extraction is performed to remove low molecular weight substances or solvents. Moreover, it is preferable to use a material in which impurities, isomers, and the like are reduced as much as possible for the compounds of the general formula (A), the general formula (B), the general formula (C), and the carbonic acid ester forming compound.
[0029]
The polycarbonate resin of the present invention has a hindered phenol-based or phosphite-based antioxidant; silicon-based, fatty acid ester-based as required in order to ensure stability and releasability required when forming a film for a flat panel display. , Fatty acid, fatty acid glyceride, beeswax and other natural oils and mold release agents; benzotriazole, benzophenone, dibenzoylmethane, salicylate, and other light stabilizers; polyalkylene glycol, fatty acid glycerides, etc. You may use an agent etc. together suitably.
[0030]
Furthermore, for the purpose of cost reduction or the like, the polycarbonate resin of the present invention and the conventional bisphenol A type polycarbonate can be arbitrarily mixed and used within a range not impairing the performance.
[0031]
When the film for flat panel display using the polycarbonate resin of the present invention is usually formed by melt extrusion film forming, it is preferably formed in the range of 230 to 380 ° C., and the melt viscosity is increased by a flow tester ( It is preferably 1 × 10 ⁻² cc / sec or more of 280 ° C., 15.7 MPa, nozzle diameter 1 mm × 10 mm). If the viscosity is less than 1 × 10 ⁻² cc / sec, extrusion is difficult because the melt viscosity is too large, and it is preferable to adjust the molding temperature and molecular weight to obtain fluidity that can be molded within a range that does not impair the physical properties.
[0032]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0033]
Example 1
9,9-bis (4-hydroxy-3-methylphenyl) fluorene (3.5 kg) (hereinafter abbreviated as BCFL) and hydrosulfite (10 g) were dissolved in 49 liters of an aqueous 8.8% (w / v) sodium hydroxide solution. . To this was added 25 liters of methylene chloride, and 2.3 kg of phosgene was blown in over 30 minutes while stirring at 15 ° C.
After the blowing, the reaction solution is emulsified by vigorously stirring for 1 minute, and 84 g of p-tert-butylphenol (hereinafter abbreviated as PTBP) and 3.5 kg of the following polysiloxane compound (hereinafter abbreviated as Si1) are added, and further stirred for 10 minutes Thereafter, 20 ml of triethylamine was added, and the mixture was further stirred for 60 minutes for polymerization.
[0034]
[Chemical Formula 10]

[0035]
The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washed repeatedly with water until the conductivity of the washing solution became 10 μS / cm 2 or less to obtain a purified resin solution. The obtained purified resin liquid was filtered through a 0.5 μm-diameter Teflon filter, and then the resin liquid was slowly added dropwise to 60 ° C. pure water that was vigorously stirred to solidify the polymer while removing the solvent. The solid was filtered and dried to obtain a white powdery polymer.
[0036]
This polymer had an intrinsic viscosity [η] at a temperature of 20 ° C. (Haggins constant of 0.45) of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent, and was 0.38 dl / g.
[0037]
300 ppm of stearic acid monoglyceride was added to the obtained polycarbonate powder, and the mixture was extruded at 280 ° C. with a vented 50 mm extruder equipped with a 50 μm polymer filter to form a melt pellet.
[0038]
The obtained pellets were extruded at 280 ° C. with a vented 90 mm melt film extruder equipped with three horizontal rolls to obtain a melt-formed film.
The thickness of the obtained polycarbonate film was 102 μm, and the thickness unevenness in the width direction was ± 3 μm.
[0039]
Example 2
Polymerization was carried out in the same manner as in Example 1 except that 2.3 kg of the following polysiloxane compound (hereinafter abbreviated as Si2) was used instead of Si1, PTBP was changed to 48 g, and 0.5 g of triethylbenzylammonium chloride was added simultaneously with the introduction of BCFL. Reaction was performed.
[0040]
Embedded image

[0041]
The intrinsic viscosity [η] of the obtained polymer was 0.28 dl / g. After pelletization in the same manner as in Example 1, the obtained melt-molded polycarbonate film had a thickness of 101 μm and a thickness unevenness in the width direction of ± 3 μm.
[0042]
Example 3
The polymerization reaction was carried out in the same manner as in Example 1 except that the polysiloxane compound was changed to 3.5 kg (hereinafter abbreviated as Si3) instead of Si1 and changed to 48 g of phenol (hereinafter abbreviated as PH) instead of PTBP.
[0043]
Embedded image

[0044]
The intrinsic viscosity [η] of the obtained polymer was 0.29 dl / g. After pelletization in the same manner as in Example 1, the thickness of the obtained melt-molded polycarbonate film was 99 μm, and the thickness unevenness in the width direction was ± 3 μm.
[0045]
Example 4
Example except that BCFL was changed to 2.5kg and Si1 to 1.8kg, and 0.62-kg of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as BPA) was added at the same time as BCFL was added. The polymerization reaction was carried out in the same manner as in 1.
The intrinsic viscosity [η] of the obtained polymer was 0.35 dl / g. After pelletization in the same manner as in Example 1, the obtained melt-molded polycarbonate film had a thickness of 101 μm and a thickness unevenness in the width direction of ± 3 μm.
[0046]
Comparative Example 1
Instead of the polycarbonate of Example 1, pelletized in the same manner as in Example 1 except that a commercially available bisphenol A type optical polycarbonate resin (Iupiro H-4000 manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used. The thickness of the obtained melt-molded polycarbonate film was 100 μm, and the thickness unevenness in the width direction was ± 3 μm.
[0047]
Comparative Example 2
Example 1 except that instead of BCFL, 9,9-bis (4-hydroxyphenyl) fluorene 0.65 kg (hereinafter abbreviated as BFL) and BPA 3.8 kg were used, PTBP was changed to 90 g, and Si1 was not used. Reaction polymerization was carried out in the same manner as described above.
The obtained polymer had an intrinsic viscosity [η] of 0.32 dl / g. After pelletization in the same manner as in Example 1, the thickness of the obtained melt-molded polycarbonate film was 102 μm, and the thickness unevenness in the width direction was ± 3 μm.
[0048]
Comparative Example 3
Instead of BCFL, use 0.87 kg of 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter abbreviated as TMBPZ) and 3.6 kg of BPA, change PTBP to 92 g, and use Si1 Reaction polymerization was carried out in the same manner as in Example 1 except that there was no reaction.
The intrinsic viscosity [η] of the obtained polymer was 0.31 dl / g. After pelletization in the same manner as in Example 1, the obtained melt-molded polycarbonate film had a thickness of 100 μm and a thickness unevenness in the width direction of ± 3 μm.
[0049]
Table 1 shows the appearance after each test of Examples 1 to 4 and Comparative Examples 1 to 3, and the transmittance results sandwiched between the polarizing plates. The measurement of the transmittance between the polarizing plates is an evaluation for confirming how much the phase difference is caused between the test pieces. A configuration in which the polarization axis and the stretching direction of the test piece (MD direction of sheet, winding direction) are sandwiched between two polarizing plates with the polarization axis aligned is (α), and the polarization axis and the stretching axis of the test piece (sheet) (Β direction, winding direction) is inclined by 45 ° and is defined as (β). Even if the test piece is polarized (phase difference), the polarization state does not collapse as long as the polarization axis coincides with the orientation axis of the resin, and there is no decrease in transmittance due to polarization (phase difference). However, when the polarization axis and the orientation axis of the resin are inclined by 45 °, a phase difference is caused, the polarization state is lost, and the transmittance is lowered. For this reason, the larger the values of (α) and (β) are, the more the sheet is polarized (phase difference).
[0050]
[Table 1]

[0051]
BCFL: 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene BPA: 2,2-bis (4-hydroxyphenyl) propane BFL: 9,9-bis (4-hydroxyphenyl) fluorene
TMBPZ: 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane intrinsic viscosity: 0.5g / 100ml dichloromethane resin solution at 20 ℃, Haggins constant 0.45, intrinsic viscosity [η] (dl / g) Asked.
Transmittance: Measured (JIS K 6714) using HGM-2DP manufactured by Suga Test Instruments Co., Ltd.
[0052]
【The invention's effect】
According to the present invention, it is possible to produce a flat panel display film having little transfer (phase difference) and excellent transferability that can impart a shape according to preference to the film surface.

Claims (8)

A polycarbonate obtained by reacting a compound represented by the general formula (A) and the general formula (B) or the general formula (A), the general formula (B), and the general formula (C) with a carbonate-forming compound. The general formula (B) is 20 to 60 wt% with respect to all monomer components [general formula (A) + general formula (B) + general formula (C)], and the intrinsic viscosity [η] is 0 A flat panel display film made of polycarbonate resin having a density of 2 to 1.0 [dl / g].

(In the formula, R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 represents an alkoxy group, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, (It can also have a C1-C5 alkoxy group.)

(In the formula, R _{5 to} R ₈ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 alkoxy groups, or aralkyl groups having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, .R ₉ to R _12, which may have an alkoxy group having 1 to 5 carbon atoms are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, carbon atoms 2 An alkenyl group having 5 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms as a substituent , An alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms .X is .R ₁₃ which may have to represent a mere bond or represents an aliphatic group having 1 to 6 carbon _{atoms, -SiO (R 14) (R} 15) - and / or -SiO (R ₁₆₎ (R ₁₇ )-represents a homopolymer, a block or a random copolymer, the degree of polymerization is 0 to 200, and R _{14 to} R ₁₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, An aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom (As a substituent, it can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group.)

(In the formula, R _{18 to} R ₁₉ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 alkoxy groups, or aralkyl groups having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, It can also have a C1-C5 alkoxy group, Y is

Wherein R ₂₀ and R ₂₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or the number of carbon atoms A group having 6 to 12 aryl groups, or a group in which R ₂₀ and R ₂₁ are bonded together to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms, and these groups have carbon atoms Can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group as a substituent. a represents an integer of 0 to 20. ) The general formula (A) is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2- The film for flat panel display according to claim 1, which is at least one selected from the group of (methylphenyl) fluorene. The film for flat panel display according to claim 1, wherein the carbonate forming compound is phosgene. The film for flat panel display according to claim 1, wherein R _{9 to} R _{12 in} the general formula (B) are at least one selected from a methyl group and a phenyl group. Random copolymer of dimethylsiloxane and diphenylsiloxane having a 3- (o-hydroxyphenyl) propyl group at the α, ω position and α, ω-bis [3- (o-hydroxyphenyl) propyl The film for flat panel display according to claim 1, which is at least one kind derived from the group of polydimethylsiloxane. The film for flat panel display according to claim 1, wherein the general formula (C) is 2,2-bis (4-hydroxyphenyl) propane. The film for a flat panel display according to claim 1, wherein the ratio of the general formula (C) is 0.5 or less in terms of the weight ratio of the general formula (C) / [general formula (A) + general formula (C)]. The flat panel display film according to claim 1, wherein a polycarbonate resin composition obtained by mixing the polycarbonate resin according to claim 1 and a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane is used.